|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
BNC4H6 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Boron
and Nitrogen |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
in 1,2-Dihydro-1,2-Azaborine
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation was made here of
the B and N nqcc tensors in BNC4H6 on molecular
structures given by (1) MP2/6-31+G(d,p) and (2) MP2/aug-cc-pVTZ
optimization. Calculated and experimental [1] are compared in
Tables 1 - 3. Structure parameters are given in
Table 4, rotational constants in
Table 5. |
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 - 3,
subscripts a,b,c refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor.
Ø (degrees) is the angle between its subscripted
parameters. ETA = (Xxx - Xyy)/Xzz. |
|
|
RMS is the root mean square
difference between calculated and experiment diagonal nqcc's (percent
of average magnitude of experimental nqcc's). RSD is the
calibration residual
standard deviation of
the model for calculation of the nqcc's. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 1. 11B
nqcc's in BNC4H6
(MHz). Calculation was made on (1) MP2/6-31+G(d,p) and (2)
MP2/aug-cc-pVTZ optimized molecular structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (1) |
|
Calc (2) |
|
Expt [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
- |
1.688 |
- |
1.695 |
- |
1.71(1) |
|
|
|
Xbb |
- |
1.423 |
- |
1.412 |
- |
1.33(2) |
|
|
Xcc |
|
3.110 |
|
3.108 |
|
3.03(2) |
|
|
|Xab| |
|
0.758 |
|
0.756 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.072 (3.6 %) |
|
0.066 (3.2 %) |
|
|
|
|
RSD |
|
0.046 (2.1 %) |
|
0.046 (2.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
- |
0.785 |
- |
0.785 |
|
|
|
|
Xyy |
- |
2.325 |
- |
2.323 |
|
|
|
|
Xzz |
|
3.110 * |
|
3.108 * |
|
|
|
|
ETA |
|
0.495 |
|
0.495 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* The z-principal axis is coincident
with the c-inertial axis, and perpendicular to the plane of the
molecule. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 2. 14N
nqcc's in 11BNC4H6
(MHz). Calculation was made on (1) MP2/6-31+G(d,p) and (2)
MP2/aug-cc-pVTZ optimized molecular structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (1) |
|
Calc (2) |
|
Expt [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
|
0.537 |
|
0.536 |
|
0.46(1) |
|
|
Xbb |
|
0.636 |
|
0.599 |
|
0.78(6) |
|
|
Xcc |
- |
1.173 |
- |
1.135 |
- |
1.25(6) |
|
|
|Xab| |
|
1.181 |
|
1.172 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.10 (12 %) |
|
0.13 (16 %) |
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
- |
0.595 |
- |
0.604 |
|
|
|
|
Xyy |
- |
1.173 |
- |
1.135 |
|
|
|
|
Xzz |
|
1.768 |
|
1.740 |
|
|
|
|
ETA |
|
0.327 |
|
0.305 |
|
|
|
|
Øz,a |
|
46.21 |
|
45.77 |
|
|
|
|
Øa,NH |
|
12.69 |
|
12.59 |
|
|
|
|
Øz,NH |
|
33.51 |
|
33.18 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 3. 10B
and 14N nqcc's
in BNC4H6
(MHz). Calculation was made on (1) MP2/6-31+G(d,p) and (2)
MP2/aug-cc-pVTZ optimized molecular structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (1) |
|
Calc (2) |
|
Expt [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa (10B)
|
- |
3.282 |
- |
3.301 |
- |
3.42(2) |
|
|
Xbb |
- |
3.168 |
- |
3.144 |
- |
1.83(5) |
|
|
Xcc |
|
6.450 |
|
6.444 |
|
5.26(3) |
|
|
|Xab| |
|
1.560 |
|
1.592 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
1.04 (29 %) |
|
1.02 (29 %) |
|
|
|
|
RSD |
|
0.102 (2.1 %) |
|
0.102 (2.1 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
Xaa (14N) |
|
0.376 |
|
0.378 |
|
0.43(1) |
|
|
Xbb |
|
0.797 |
|
0.757 |
|
0.79(3) |
|
|
Xcc |
- |
1.173 |
- |
1.135 |
- |
1.22(3) |
|
|
|Xab| |
|
1.163 |
|
1.157 |
|
|
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
0.04 (5.1 %) |
|
0.06 (7.4 %) |
|
|
|
|
RSD |
|
0.030 (1.3 %) |
|
0.030 (1.3 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
| Table 4.
BNC4H6. Heavy atom structure
parameters
(Å
and degrees). (1) MP2/6-31+G(d,p) and (2)
MP2/aug-cc-pVTZ optimized molecular structures.
Complete structures are given here
in Z-matrix format. |
| |
|
|
|
|
|
ropt(1) |
ropt(2) |
|
|
|
|
|
C(6)B |
1.5147 |
1.5121 |
| BN |
1.4384 |
1.4362 |
| NC(3) |
1.3696 |
1.3633 |
| C(3)C(4) |
1.3736 |
1.3692 |
| C(4)C(5) |
1.4207 |
1.4156 |
| C(5)C(6) |
1.3839 |
1.3798 |
| C(6)BN |
114.36 |
114.26 |
| BNC(3) |
124.07 |
124.07 |
| NC(3)C(4) |
120.36 |
120.46 |
| C(3)C(4)C(5) |
120.40 |
120.37 |
| C(4)C(5)C(6) |
121.61 |
121.68 |
|
C(5)C(6)B |
119.20 |
119.16 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 5. 11BNC4H6.
Rotational constants (MHz). (1) MP2/6-31+G(d,p) and (2)
MP2/aug-cc-pVTZ optimized molecular structures. |
| |
|
|
|
|
|
|
ropt(1) |
ropt(2) |
Expt [1] |
|
|
|
|
|
|
A |
5636.2 |
5668.5 |
5657.335(1) |
|
B |
5355.6 |
5383.6 |
5349.2807(5) |
|
C |
2746.2 |
2761.2 |
2749.1281(4) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] A.M.Daly, C.Tanjaroon,
A.J.V.Marwitz, S.-Y.Liu, and S.G.Kukolich, J.Am.Chem.Soc.
132(15),5501(2010). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Nitrogen |
|
|
|
|
|
Molecules/Boron |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
BNC4H6.html |
|
|
|
|
|
|
Last
Modified 14 June 2010 |
|
|
|
|
|
|
|
|
|
|